Dyeing human hair with oxidation bases and an indoline coupler

ABSTRACT

Keratinic fiber dye compositions comprising a para or ortho diamino or amino-hydroxy aromatic or heterocyclic oxidation dye and an indoline derivative coupling agent; and the process of dyeing human hair with this composition and an oxidizing agent.

United States Patent Kalopissis et al.

DYEING HUMAN HAIR WITH OXIDATION BASES AND AN INDOLINE COUPLERInventors: Gregoire Kalopissis, Paris; Andree Bugaut,

Boulogne sur Seine; Hubert Gaston- Breton, Paris, all of FranceAssignee: Soeiete Anonyme dite: LOreal, Paris,

France Filed: May 8, 1969 Appl. No.: 823,168

Foreign Appliultion Priority Data May 17, 1968 France ..56l02 US. Cl..8/10.2, 8/11, 8/32 Int. Cl.

Field of Seal'th ..8/l0.2, 11; 96/100;

[451 Mar. 14, 1972 Primary Examiner-Albeit T. Meyers AssistantExaminer-Vera C. Clarke Anomey-Holcombe, Wetherill and BriseboisABSTRACT Keratinic fiber dye compositions comprising a para or orthodiamino or amino-hydroxy aromatic or heterocyclic oxidation dye and anindoline derivative coupling agent; and the process of dyeing human hairwith this composition and an oxidizing agent.

4 Claims, No Drawing DYEING HUMAN HAIR WITH OXIDATION BASES AND ANINDOLINE COUPLER SUMMARY OF THE INVENTION Compositions comprisingoxidation dyes, and particularly orthoor para-diamine or orthoorpara-amino-hydroxyl derivatives of aromatic or heterocyclic nuclei, arecommonly used to dye human hair. in order to vary the shades obtained byusing these bases, it has already been suggested that color modifiers orcouplers may be used, and particularly aromatic metadiamines, metaaminophenols, di-ketones, and pyrazolones.

The present invention relates to a new class of couplers which may beused with known oxidation dyes. The couplers are known compounds, buthave not heretofore been used as couplers with oxidation dyes.

It is a further object of the present invention to provide the newarticle of manufacture which consists of a composition for dyeingkeratinic fibers and particularly human hair, which is essentiallycharacterized by the fact that it contains:

1. At least one base consisting of an oxidation dye selected from thegroup consisting of those compounds the molecule of which includes anaromatic or heterocyclic nucleus carrying two amino groups or an aminogroup and a hydroxyl group in ortho or para position with respect toeach other;

2. At least one coupler consisting of an indoline corresponding to thegeneral formula:

l s.-. E. wuss in which R and R represents a hydrogen atom or a loweralkyl radical having one to six carbon atoms, X represents a hydroxylradical or an amino radical when X represents a hydrogen atom, and viceversa, X represents a hydroxyl radical or an amino radical when Xrepresents a hydrogen atom, R represents a hydrogen atom or a loweralkyl radical, but necessarily representing a hydrogen atom when X isdifferent from a hydrogen atom. The coupler may also be an acid salt ofsuch an indoline, and specifically a halohydric acid salt.

Among the bases which may advantageously be used with the couplersaccording to formula I are:

para-phenylenediamine, para-tolylenediamine, paraaminophenol,N-methyl-para-aminophenol, chloro-paraphenylenediamine,methoxy-para-phenylenediamine, 6-methoxy-3-methyl-para-phenylenediamine, (N-ethyl-N-carbamylmethyl)-para-phenylenediamine, and 2,5- diaminopyridine.

Among the couplers responding to the above formula are:

6-aminoindoline dihydrochloride; o-hydroxyindoline hydrochloride;l-ethyl-o-aminoindoline dihydrochloride; and l-N-ethyl-4-hydroxyindolinehydrobromide. Other suitable couplers are the hydrochlorides anddihydrochlorides of l-methyl-4-hydroxyindoline, oflethyl--hydroxyindoline, or l-methyl-6-hydroxyindoline and of2-methyl-6-aminoindoline.

In the hair-dyeing compositions according to the invention the molarratio of base to coupler may vary from 1:1 to 1:3, but more coupler thanbase is preferred.

It is important to avoid using an excess of base with respect to thecoupler because the base has a tendency to become colored itself, whichleads to the superposition of two colors and a defective result. Inorder to obtain a color resulting solely from the interaction of baseand coupler, it is therefore necessary to have as much coupler as base.

The dyeing composition according to the invention may contain other dyeswhich may be used under the same conditions, such as direct dyes (forexample, azo dyes, anthraquinone dyes, and metalliferous dyes) and dyesformed by combining bases and couplers other than those forming thesubject matter of the present invention.

The composition according totheinvention may also contain wettingagents, dispersing agents, penetratingagents, or ingredientsconventionally used indyeing hair. They may take the form of an aqueoussolution, a cream,-a gel or an aerosol.

The dyeing composition is used in a conventional manner at an alkalinepH, between 9 and 10 inclusive. This pH value :may be obtained by addingammonia. At a pH below 9 coupling is too slow and an unsatisfactorycolor results. At above l0 the skin may be irritated. The composition isapplied to the hair in the presence of an oxidizing solution suitablefor use on human hair and other keratinic fibers, which is preferably ahydrogen peroxide solution.

The compositions according to the invention lead to dyes affording abroad range of colors and having the advantage that they do not changecolor when exposed to the light or to inclement weather and adherefirmly to the hair.

The following examples are given purely by way of illustration:

EXAMPLE I The following dyeing solution is prepared:

N-ethyl-4-hydroxyindoline hydrobromide l,4-diamino-2-methoxybenzene lg.lg.

Resorcin 0.3 g. Para-tolylenediamine 0.2 g. 20% ammonia l0 cc. Sodiumsulfite 0.5 g. Ethylenediarninetetraacetic acid 0.2 g. 20% lauryl,ammonium sulfate 20 g. Water, q.s.p. I00 g.

This solution is mixed with an equal quantity of 6% hydrogen peroxide.When this is applied to l00% white hair, the hair is well covered with along lasting green color at the end of 30 minutes.

EXAMPLE 2 The following dyeing solution is prepared:

This solution, when mixed with an equal quantity of 6% hydrogenperoxide, and applied to white hair for half an hour, imparts thereto anintense teal blue, which is light-stable.

EXAMPLE 3 The following dyeing solution is prepared:

N-ethyl-4-l1ydroxyindoline hydrobromide l.5 g. Para-lolylenediamine 0.7g. Resorcin 0.2 g. 20% ammonia l0 cc. Sodium sulfite 0.5 g.Ethylenediaminetetraacetic acid 0.2 g. 20% lauryl ammonium sulfate 20 g.Water q.s.p. I00 g.

This solution is mixed with an equal quantity of 6% hydrogen peroxide.When applied to white hair for half an hour, it imparts thereto a deepchestnut coloration.

EXAMPLE 4 The following hair dyeing solution is prepared:

b-aminoindoline Para-aminophenol l.5 g. l g.

Rcsorcin 0.5 g. 20% ammonia cc. Sodium sull'ite 0.5 g.Ethylcnediaminetctraacetic acid 0.2 g. 20% lauryl ammonium sulfate 20Water q.s.p. 100 g.

This solution is mixed with an equal quantity of 6% hydrogen peroxide.When applied to 100% white hair for a period of 30 minutes, the resultis a mahogany coloration.

EXAMPLE 5 The following dyeing solution is prepared:

6-aminoindolinc L5 Para-tolylenediaminc 1.2 g. 20% ammonia cc. Sodiumsulfite 0.5 g. Ethylcnediaminetetraacetic acid 0.2 g. lauryl ammoniumsulfate 20 Water qsp. 100 g.

This solution, when mixed with an equal quantity of 6% hydrogenperoxide, and applied for half an hour to white hair, produces ablue-black coloration.

EXAMPLE 6 The following dyeing solution is prepared:

Para-tolylenediamine l g.

Para-aminophenol 0.5 g. Resorcin 0.l g. fi-aminoindoline dihydrochloride2 g. Lauryl ammonium sulfate with 20% fatty alcohol 20 g.Ethylenediaminetetraacctic acid sold under the trademark TRILON B 0.3 g.20% ammonia 10 g. 40% sodium bisullite l g. Water q.s.p. F E 100 g.

This solution when mixed with an equal weight of 6% hydrogen peroxideand applied for about minutes to 100% white hair, produces a goldenchestnut coloration.

EXAMPLE 7 The following dyeing solution is prepared:

Para-tolylencdiaminc Para-aminophenol 0.5 g Rcsorcin 0.] g6-hydroxyindolinc hydrochloride 2 g Lauryl ammonium sulfate with 20%fatty alcohol 20 g Ethylenediaminetctraacctic acid sold under the tradename TRILON B 0.3 g. 20% ammonia 10 g. 40% sodium bisulfitc l g. Waterqsp. 100 g.

This solution, when mixed with an equal weight of 6% hydrogen peroxideand applied for 30 minutes to 100% white hair, produces a goldenchestnut coloration.

EXAMPLE 8 The following dyeing solution is prepared:

Para-tolylcnediamine l g. Paru-aminuphenol 0.5 g. Resorcin 0.1 g,l-ethyl6-aminoindolinc dihydrochloride 2 g. Lauryl ammonium sulfate with20% fatty alcohol 20 g l'ilhylcncdiaminctctruucclic acid.

sold under the trade name TRILON B 0.3 g. 20% ammonia 10 g. 40% sodiumhisullitc l g. Water qsp. W0 5.

This solution, when mixed with an equal quantity of 6% hydrogenperoxide, and applied for 30 minutes to white hair, produces a goldenchestnut coloration.

What is claimed is:

l. A process for dyeing hair comprising applying to said hair in amountseffective to dye said hair a hair dye composition comprising an aqueoussolution of an oxidation dye having a nucleus selected from the groupconsisting of phenyl and pyridine carrying as substituents in ortho orpara position to each other 1) two amino or (2) one amino and onehydroxy, and an indoline coupler having the formula wherein R and R eachindependently are selected from the group consisting of hydrogen andlower alkyl, one of X. and X is selected from the group consisting ofhydroxy and amino and the other is hydrogen and R. is selected from thegroup consisting of hydrogen and lower alkyl and must be hydrogen when Xis other than hydrogen, the mole ratio of said oxidation dye to saidcoupler ranging between 1:1 to 1:3, said composition being applied inthe presence of hydrogen peroxide as an oxidizing agent.

2. The process of claim 1 wherein said hair dye composition has a pH of9l0.

3. The process of claim 1 wherein said oxidation dye is selected fromthe group consisting of para-phenylenediamine, para-tolylenediamine,para-aminophenol, N-methyl-paraaminophenol,chloro-para-phenylenediamine, methoxyparaphenylenediamine,o-methoxy-3-methyl-para-phenylenediamine (N-ethyl-N-carbamylmethyl)-para-phenylenediamine, l,4-diamine-Z-methoxybenzene, l,4-diamino-Z-methoxy-S-methylbenzene and 2,5-diaminopyridine.

4. The process of claim 1 wherein said coupler is selected from thegroup consisting of o-hydroxyindoline hydrochloride,l-ethyl-fi-aminoindoline dihydrochloride, I-N- ethyl-4-hydroxyindolinehydrobromide, o-aminoindoline and its dihydrochloride, the hydrochlorideand dihydrochloride of l-methyl-4-hydroxyindoline, ofl-ethyl-6-hydroxyindoline, of l-methyl-6-hydroxyindoline and2-methyl-6-aminoindoline.

2. The process of claim 1 wherein said hair dye composition has a pH of9-10.
 3. The process of claim 1 wherein said oxidation dye is selectedfrom the group consisting of para-phenylenediamine,para-tolylenediamine, para-aminophenol, N-methyl-para-aminophenol,chloro-para-phenylenediamine, methoxypara-phenylenediamine,6-methoxy-3-methyl-para-phenylenediamine,(N-ethyl-N-carbamylmethyl)-para-phenylenediamine,1,4-diamine-2-methoxybenzene, 1,4-diamino-2-methoxy-5-methylbenzene and2,5-diaminopyridine.
 4. The process of claim 1 wherein said coupler isselected from the group consisting of 6-hydroxyindoline hydrochloride,1-ethyl-6-aminoindoline dihydrochloride, 1-N-ethyl-4-hydroxyindolinehydrobromide, 6-aminoindoline and its dihydrochloride, the hydrochlorideand dihydrochloride of 1-methyl-4-hydroxyindoline, of1-ethyl-6-hydroxyindoline, of 1-methyl-6-hydroxyindoline and2-methyl-6-aminoindoline.